Resin-forming reaction of phenol, aldehyde, and amine in presence of polyhalophenol



Patented Mar. 20, 1951 UNITED STATE S PATENT 'OFFICEJQ Clyde E. Gleim,Akron, Ohio, assignor to Wingfoot Corporation, Akron, Ohio, acorporation of Delaware No Drawing. Application January 10, 1947, SerialNo. 721,467

3 Claims. (Cl. 26045) 3 This invention relates to the use ofpolyhalophenols as a catalyst in the reaction of a mixture of a phenol,an aldehyde and an amine and more particularly to the use ofpolyhalophenols as an agent for advantageously modifying thecharacteristics of the product resulting from the reaction of thismixture.

It has been discovered that the time required to complete the reactionof a mixture comprising a phenol, an aldehyde and an amine may beconsiderably reduced when the reaction is carried @out .in the presenceof a polyhalophenol. It has been particularly observed that thiscatalytic function of the polyhalophenol is most pronounced when using apolyhalophenol containing at least 4 halogen atoms and not more thanhalogen atoms. Therefore, the most desirable catalytical efiect isobservedwhen using those polyhalophenols containing 4 or 5 halogenatoms.

2 tive ratios of phenolic compound to amine compound are 1/80; 1/1; /1;and 4/1. The catalytic effect of the polyhalophenol is most pronouncedwhen the phenol is present in an amount ranging from about 1/2 to 2/ 1mol of the amine.

The ration of the aldehyde to the reactants, including the phenol andthe amine, is not particularly limited. Usually, ,molar ratios ofaldehyde to reactants are those ranging from about 3 /4 to about 5/4.The particular amount of reactants to be employed is dependent in eachcas upon the type of product desired.

Any phenol may be used in carrying out the reaction of this inventionand includes phenol, the cresols, phenol-cresol mixtures, the xylenols,resorcinol, hydroquinone, alpha naphthols, beta naphthols, etc.

Any aldehyde may be used, including formaldehyde, acetaldehyde,butyaldehyde, propionalde- The catalytic characteristics of thepolyhalo- 2o hyde, furfurylaldehyde, etc. phenols are observed whenreacting a mixture Any amine may be used, including the arylcontainingany phenol, any aldehyde and any amines, such as aniline, 0-, m-, orp-toluidines or amine. These polyhalophenols do not appear to mixedtoluidines, p,p-diaminodiphenyl methane, be catalytic when added to aphenol-aldehyde etc.; the saturated cyclic amines such as cyclomixturewhich does not contain an amine. When hexylamine; and the heterocyclicamines such as the polyhalophenol is present in a concentrationfurfurylamine. The primary amines are of parof as little as 0.005 moland up about 0.15 mol ticular value. per mol of reactants including thephenol and. The catalytic efiect of these polyhalophenols is the amine,the effect observed is primarily to rebest illustrated by the followingformulations in duce the time necessary to bring the reaction to which50 poundsof a phenol-aniline-formaldecompletion. It is preferred to useabout 0.01 mol hyde resin was produced first without the aid of of thepolyhalophenol per mol of the reactants pentachlorophenol, and thenusing pentachlorowhen the efiect desired is reduction in reactionphenol. Thus, a mixture comprising 0.50 mol of time. Largerconcentrations of polyhalophenol phenol, 0.5 mol of aniline, 0.84 mol offormalin produces the same desired catalytic effect and, in (37%formaldehyde) and 2 ml. of 4 N sulfuric addition, modifies the endproduct depending acid was reacted to completion in a total reactionupon the amount of polyhalophenol employed. time of 43-45 minutes. Theaddition of 0.01 mol Therefore, when it is desired to modify the charofpentachlorophenol caused this same mixture to acteristics of the productresulting from the rego to completion using the same conditions ofaction of a mixture of a phenol, an aldehyde and heating in a totalreaction time of only 17 minan amine, thena catalytic quantity greaterthan utes. 0.15 mol of the polyhalophenol should be used. The followingadditional examples emphasize The molar ration of the phenolic compoundto the value of the various polyhalophenols as catathe amine compound inthe presence of an aldelysts in this reaction and the effect producedunhyde'may vary from 1/ 100 to 100/1. Representader varying conditions:

* Table MOFS' MOP 4N Catalyst MOFS Reaction Time 0 O Aniline PhenolH1804 Moles Kind E mMinutes Ml. 2 1.0 None 2 1.0 p-chlorophenol 1.68A-40; (3-65. 3 1.0 0. 98 2 0.2 2,4-dichlorophenol 17 68 A-40; (3-80. 41.0 0. 98 2 .02 2,4,5-trichl01ophenoL 1.68 A-37; (3-52. 5 1.0 0.98 2 .022,3,4,fi-tetrachlorophenOL l. 68 A-20; C-25. 6 1.0 0. 98 2 ..022,3,4,5,6-pentachlorophenol 1.68 A-20; (3-25. 1 1.0 0. 98 None .02 do1.68 A-17; e-25. 8 1.0 0. 95 2 .05 do 1.68 A-ll; o-11. 9 1.0 0.90 None.1 do 1.68 A1l;C-16. 10 1.0 0. 98 None .02 hexachlorophenoL l. 68Al;O-180. n 1.0 1.0 None NH4OH 1. 68 A-a0; C-65. 12 1.0 1.0 1. 0s A-35;04s.

The reaction time measured when using a polyhalophenol was first thetotal reaction time comprising the time elapsed from the moment the fourcomponents had been brought together until the desired product wasproduced and is indicated at C. The time elapsed from the time themixture had first reached reflux conditions until the reaction wascompleted is indicated at A.

Best results with respect to total reaction time is obtained when usingthe tetra and penta chlorophenols, and particularly the 2,3,4,6-tetrachlorophenol, and the 2,3,4,5,6-pentachlorophenol. Less desirable resultsare produced when using the halophenols having less than 4 halo atoms.

As pointed out before, a catalytic quantity of the polyhalophenolgreater than 0.15 mol per mol of reactants, may be successfully used.However, when these larger concentrations are used, the resulting resinsare generally insoluble in the common organic solvents, a characteristicnot observed when using catalytic amounts less than 0.15 mol of thepolyhalophenol. This insolubilizing eifect is noticed when about 0.15mol or more of polyhalophenol is used per mol of reactants. However,these polyhalophenol modified phenolic resins are soluble in dilutealkalis. These resins containing the higher concentrations of-polyhalophenols may be used as a spray or in powder form as aninsecticide and as a weed killer. These resins may also be used incoating compositions and find particular use in the molding art, andresist burning when heated.

The resins produced when using an amount smaller than about 0.15 mol ofthe polyhalophenol may be used in producing molded articles and asintermediates in the production of other useful resin-forming materials.

Suitable changes may be made in the details of the process withoutdeparting from the spirit or scope of the present invention, the proper4 limits of which are defined in the appended claims.

I claim: 1. The method of forming a resin which comprises reacting amixture of phenol, an aldehyde and an amine selected from the groupconsisting of primary arylamines, cyclohexylamine, and furfuryl amine inthe presence of a catalytic amount, from 0.005 to 0.15 mol per mol ofreactants, of a polyhalophenol selected from the group consisting oftetrachlorophenol and pentachlorophenol.

2. The method of forming a resin which comprises reacting a mixture ofphenol, formaldehyde, and aniline in the presence of a catalytic amount,from 0.005 to 0.15 mol per mol of reactants, of a polyhalophenolselected from the group consisting of tetrachlorophenol andpentachlorophenol.

3. The method of forming a resin which comprises reacting a mixturecomprisingd to 1 mol of phenol, formaldehyde, and ,1 to 1 mol of anamine selected from the group consisting of primary arylamines,cyclohexylamine, and iurfuryl amine in the presence of 0.005 to 0.15 molof a polychlorophenol selected from the group .consisting oftetrachlorophenol and pentachlorophenol.

CLYDE E. GLEIM.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS

1. THE METHOD OF FORMING A RESIN WHICH COMPRISES REACTING A MIXTURE OFPHENOL, AN ALDEHYDE AND AN AMINE SELECTED FROM THE GROUP CONSISTING OFPRIMARY ARYLAMINES, CYCLOHEXYLAMINE, AND FURFURYL AMINE IN THE PRESENCEOF A CATALYTIC AMOUNT, FROM 0.005 TO 0.15 MOL PER MOL OF REACTANTS, OF APOLYHLOPHENOL SELECTED FROM THE GROUP CONSISTING OF TETRACHLOROPHENOLAND PENTACHLOROPHENOL.